Activating composition of metallocene complexes in the catalysis of (co)polymerization processes of olefins

Abstract

An organometallic composition of a reaction product of a fluorinated organic compound of formula (I):wherein R1 to R8 are as described in the specification, m is 0 or 1; and an organometallic compound of formula (II):wherein M', R, X, n and p are as described in the specification; a polymerization catalyst composition using the above organometallic composition and a metallocene complex a method of making the catalyst composition and using the catalyst composition to polymerize alpha-olefins.

What is claimed is:  
     
       1. An organometallic composition comprising the reaction product between: 
       (A) a fluorinated organic compound of formula (I):                    
       wherein each R 1  to R 7  group is a substituent independently selected from the group consisting of hydrogen, fluorine, a fluorinated or non-fluorinated, aliphatic hydrocarbyl group and a fluorinated or non-fluorinated aromatic hydrocarbyl group, having from 1 to 20 carbon atoms, optionally joined to a different hydrocarbyl group to form a further cycle,  
       on the condition that at least two of the groups R 1  to R 5  are independently selected from the group consisting of:  
       fluorine,  
       a fluorinated alkyl group having the formula —CF(R 9 R 10 ), wherein each R 9  or R 10  group is a substituent independently selected from the group consisting of hydrogen, fluorine, a fluorinated or non-fluorinated, aliphatic hydrocarbyl group and a fluorinated or non-fluorinated aromatic hydrocarbyl group, having from 1 to 20 carbon atoms, optionally joined to a different hydrocarbyl group to form a further cycle and at least one of them is fluorine, or fluorinated alkyl at least in position 1, or a fluorinated aryl Ar F  as defined below, or a fluorinated vinyl group V F  as defined below, or a fluorinated aryl group Ar F  substituted on the aromatic ring with at least two groups selected from fluorine, a —CF(R 9 R 10 ) group as defined above or a different Ar F  group, or  
       a fluorinated vinyl group V F  substituted on at least two positions of the double bond with groups selected from the group consisting of fluorine, a —CF(R 9 R 10 ) group and an Ar F  group as defined above;  
       the R 8  group is hydrogen, —OH, —SH, or, together with the R 5  group forms a carbonyl oxygen; and  
       m is 0 or 1;  
       (B) an organometallic compound of formula (II)  
       
         
           M′R n X (p−n)   (II)  
         
       
       wherein M′ is a metal of group 2 or 13 of the periodic table of elements; each R is independently a hydrocarbyl group having from 1 to 10 carbon atoms; each X is a halogen atom; p is 2 for group 2 and 3 for group 13, n is a decimal number ranging from 1 to p.  
     
     
       2. The organometallic composition according to  claim 1 , wherein M′ is Mg or Al and X is chlorine or bromine. 
     
     
       3. The composition according to  claim 1 , wherein M′ is Al, p=n=3 and R is alkyl. 
     
     
       4. The composition according to  claim 1 , wherein m is zero. 
     
     
       5. The composition according to  claim 1 , wherein R 5  is fluorine or fluorinated aryl. 
     
     
       6. The composition according to  claim 1 , wherein R 8  is hydrogen. 
     
     
       7. The composition according to  claim 1 , wherein R 8  is a hydroxy group. 
     
     
       8. The composition according to  claim 1 , wherein said fluorinated organic compound has formula (IV):                    
       wherein 
       R 5  and R 8  have the same meaning as defined for formula (I),  
       y and z independently range from 1 to 4,  
       R 11  and R 12  are independently selected from the group consisting of fluorine, a fluorinated or non-fluorinated aliphatic hydrocarbyl group and a fluorinated or non-fluorinated aromatic hydrocarbyl group, having from 1 to 20 carbon atoms, optionally joined to a different R 11  or R 12  hydrocarbyl group, respectively, to form another cycle,  
       on the condition that at least 3 of the groups R 5 , R 11  and R 12  are independently selected from the group consisting of:  
       fluorine,  
       a fluorinated alkyl group having the formula —CF(R 9 R 10 ) wherein each R 9  or R 10  group has any of the above meanings of R 1  to R 7  groups of  claim 1  and at least one of these is fluorine, or fluorinated alkyl at least in position 1, or a fluorinated aryl Ar F  as defined below, or a fluorinated vinyl group V F  as defined below, or  
       a fluorinated aryl Ar F  substituted on the aromatic ring with at least two groups selected from the group consisting of fluorine, a —CF(R 9 R 10 ) group as defined above and a different Ar F  group, or  
       a fluorinated vinyl group V F  substituted on at least two positions of the double bond with groups selected from the group consisting of fluorine, a —CF(R 9 R 10 ) group and an Ar F  group as defined above in  claim 1 .  
     
     
       9. The composition according to  claim 8 , wherein all eight R 11  and R 12  are the same and are trifluoromethyl or fluorine. 
     
     
       10. The composition according to  claim 1 , wherein components (A) and (B) are in such a quantity that the ratio between M′ and said compound of formula (I) ranges from 0.1 to 100. 
     
     
       11. A catalytic composition comprising the following components in contact with each other: 
       (i) the organometallic composition according to  claim 1 ,  
       (ii) a metallocene complex of a metal M of group 4 of the periodic table, comprising at least one cyclopentadienyl group, optionally substituted, pentahapto(η 5 -) coordinated to said metal.  
     
     
       12. The catalytic composition according to  claim 11 , wherein said components (i) and (ii) are in such a quantity that the molar ratio (A)/(M), wherein (M) are the moles of metal in component (ii) and (A) the moles of di-unsaturated compound in the organometallic composition (i), ranges from 0.5 to 50. 
     
     
       13. The catalytic composition according to  claim 11 , wherein said metallocene complex (ii) has the following formula (III):                    
       wherein: 
       M represents a metal selected from the group consisting of Ti, Zr and Hf;  
       each R A  independently represents an anionic group bound to the metal M, different from cyclopentadienyl or substituted cyclopentadienyl;  
       w is an integer of 1 or 2, depending on whether the valence of M is 3 or 4;  
       A represents an anionic ligand having from 5 to 30 carbon atoms comprising an η 5 -cyclopentadienyl ring coordinated to the metal M;  
       R B , regardless of the nature of the other substituents, has any of the meanings previously specified for the ligand A and for the group R A , and can also be connected with said group A by means of a divalent organic group having from 1 to 15 carbon atoms, to form a bridged metallocene complex.  
     
     
       14. The catalytic composition according to  claim 13 , wherein, in said metallocene complex having formula (III), the groups R A  and R B  are independently selected from the group consisting of hydride, chloride, bromide, a hydrocarbyl or halogenated hydrocarbyl radical, different from cyclopentadienyl, having from 1 to 30 carbon atoms, a phosphonate, sulfonate or carbonate group, an alkoxy, carboxy or aryloxy group having from 1 to 20 carbon atoms, an amide group, an organic group having from 1 to 20 carbon atoms bound to the metal M with an amide nitrogen atom, and an organic group having from 1 to 20 carbon atoms, bound to the metal M with a silicon atom. 
     
     
       15. The catalytic composition according to  claim 11 , wherein said metallocene complex (ii) has the following formula (V):                    
       wherein: 
       M represents a metal selected from the group consisting of titanium, zirconium and hafnium;  
       A′ and A″ independently represent an anionic group containing an η 5 -cyclopentadienyl ring coordinated to the metal M;  
       R′ and R″ independently is selected from the group consisting of hydride, chloride, bromide, a C 1 -C 20  alkyl or alkylaryl group, a C 3 -C 20  alkylsilyl group, a C 5 -C 20  cycloalkyl group, a C 6 -C 20  aryl or arylalkyl group, a C 1 -C 20  alkoxyl or thioalkoxyl group, a C 2 -C 20  carboxylate or carbamate group, a C 2 -C 20  dialkylamide group and a C 4 -C 20  alkylsilylamide group.  
     
     
       16. The catalytic composition according to  claim 15 , wherein, in said metallocene complex having formula (V), the groups A′ and A″ are cyclopentadienyl, indenyl, or fluorenyl, wherein one or more carbon atoms of their molecular skeletons are substituted with a linear or branched, alkyl, aryl or alkylsilyl radical having from 1 to 10 carbon atoms. 
     
     
       17. A method for the preparation of the catalytic composition according to  claim 13 , comprising putting components (i) and (ii) in contact with each other, so that the ratio (A)/(M), wherein (M) are the moles of metallocene complex having formula (III) and (A) the moles of fluorinated compound having formula (I) in  claim 1 , ranges from 0.5 to 50. 
     
     
       18. The method according to  claim 17 , wherein said components (i) and (ii) are put in contact and reacted with each other in an inert diluent and at temperatures ranging from room temperature up to 150° C., for times varying from 1 to 30 minutes. 
     
     
       19. The method according to  claim 17 , wherein said metallocene complex in component (ii) consists of a complex having formula (III) wherein R A  and R B  are both different from alkyl, comprising the step of reacting said metallocene complex with a quantity of said organometallic compound having formula (II) sufficient to effect the alkylation of said metallocene complex. 
     
     
       20. The method according to  claim 19 , wherein the metal M′ in the compound having formula (II) is Mg and the atomic ratio M′/M ranges from 3 to 10. 
     
     
       21. A process for the (co)polymerization of one or more α-olefins, both in continuous and batch, in one or more steps in suitable reactors, at 0.1-1.0 MPa, 1.0-10 MPa or 10-150 MPa pressure, at temperatures ranging from 20 to 240° C., optionally in the presence of an inert diluent, wherein said one or more α-olefins are (co)polymerized, under one of the above conditions, in the presence of a catalytic composition according to  claim 11 . 
     
     
       22. The process according to  claim 21 , wherein ethylene is co-polymerized with at least one α-olefin having from 3 to 10 carbon atoms. 
     
     
       23. The process according to  claim 22 , wherein, in addition to said at least one α-olefin, an aliphatic or alicyclic, non-conjugated diene having from 5 to 20 carbon atoms, is copolymerized with ethylene. 
     
     
       24. The process according to  21 , wherein said process is carried out in a solution or suspension in a suitable inert liquid medium consisting of an aliphatic or cycloaliphatic hydrocarbon having from 3 to 15 carbon atoms, or a mixture of these. 
     
     
       25. The process according to  claim 21 , wherein said catalytic composition is prepared separately and subsequently put in contact with said one or more α-olefins. 
     
     
       26. The process according to  claim 21 , wherein said catalytic composition is prepared in situ in said process. 
     
     
       27. The composition according to  claim 1 , wherein components (A) and (B) are in such a quantity that the ratio between M′ and said compound of formula (I) or (IV) ranges from 1 to 10. 
     
     
       28. The composition according to  claim 8 , wherein at least 4 of the groups R 5 , R 11  and R 12  are independently selected from the group consisting of: 
       fluorine,  
       a fluorinated alkyl group having the formula —CF(R 9 R 10 ) wherein each R 9  or R 10  group can have any of the above meanings of R 1  to R 7  groups of  claim 1  and at least one of these is fluorine, or fluorinated alkyl at least in position 1, or a fluorinated aryl Ar F  as defined below, or a fluorinated vinyl group V F  as defined below, or  
       a fluorinated aryl Ar F  substituted on the aromatic ring with at least two groups selected from the group consisting of fluorine, a —CF(R 9 R 10 ) group as defined above and a different Ar F  group, or  
       a fluorinated vinyl group V F  substituted on at least two positions of the double bond with groups selected from the group consisting of fluorine, a —CF(R 9 R 10 ) group and an Ar F  group as defined above.  
     
     
       29. The composition according to  claim 1 , wherein at least three of the groups R 1  to R 5  are independently selected from the group consisting of: 
       fluorine,  
       a fluorinated alkyl group having the formula —CF(R 9 R 10 ), wherein each R 9  or R 10  group has any of the above meanings of the R 1  to R 7  groups in  claim 1  and at least one of them is fluorine, or fluorinated alkyl at least in position 1, or a fluorinated aryl Ar F  as defined below, or a fluorinated vinyl group V F  as defined below, or a fluorinated aryl group Ar F  substituted on the aromatic ring with at least two groups selected from the group consisting of fluorine, a —CF(R 9 R 10 ) group as defined above and a different Ar F  group.  
     
     
       30. The composition according to  claim 8 , wherein all eight R 11  and R 12  are the same and are fluorine.